Oxazolidine derivatives

ABSTRACT

A fungicidal method employing N-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione as the active ingredient.

This is a division of application Ser. No. 473,505, filed May 28, 1974.

The present invention relates to new and valuable oxazolidinederivatives having good fungicidal properites; fungicides containingthese compounds as active ingredients; and the use of these compounds asfungicides.

It is known that N-3,5-dichlorophenyloxazolidines, e.g.N-3,5-dichlorophenyl-5,5-dimethyloxazolidine-2,4-dione, may be used asfungicides. However, they only have a poor fungicidal action.

We have now found that oxazolidine derivatives of the formula ##SPC1##

Where R¹ and R² are identical or different and each denotes haloalkenylor alkenyl, R¹ additionally denotes hydrogen or alkyl of 1 to 4 carbonatoms, or R¹ and R² together denote methylene, have a good fungicidalaction which is superior to that of prior art compounds.

Examples of compounds according to the invention are as follows:

N-(3,5-dichlorophenyl)-5-methyl-5-(1-bromovinyl)-oxazolidine-2,4-dione;

N-(3,5-dichlorophenyl)-5-methyl-5-(2-bromopropenyl)-2,4-oxazolidinedione;

N-(3,5-dichlorophenyl)-5-(3-bromopropen-1-yl)-2,4-oxazolidinedione;

N-(3,5-dichlorophenyl-5-methyl-5-vinyloxazolidine-2,4-dione;

N-(3,5-dichlorophenyl)-5-methyl-5-propenyloxazolidine-2,4-dione;

N-(3,5-dichlorophenyl)-5-methyl-5-(2,2-dimethylvinyl)-oxazolidone-2,4-dione;

N-(3,5-dichlorophenyl)-5-propenyl-5-vinyloxazolidine-2,4-dione;

N-(3,5-dichlorophenyl)-5-methyleneoxazolidine-2,4-dione, m.p. 141° C.

the new compounds have a very good action on phytopathogenic fungi andon the following fungi which destroy industrial products such astextiles, surface coatings and materials containing cellulose:

Erysiphe graminis

Erysiphe cichoriacearum

Botrytis cinerea

Monilia fructigena

Piricularia oryzae

Pellicularia filamentosa

Sclerotinia sclerotiorum

Aspergillus niger

Chaetomium globosum.

The compounds are particularly suitable for preventing and curing plantdiseases caused by fungi.

The agents according to the invention may be used as solutions,emulsions, suspensions or dusts. The form of application dependsentirely on the purpose for which the agents are being used; in any caseit should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbonshaving boiling points higher than 150° C, e.g. tetrahydronaphthalene oralkylated naphthalene, or organic liquids having boiling points higherthan 150° C and having one or more than one functional group, e.g. theketo group, the ether group, the ester group or the amide group, thisgroup or these groups being attached as substituent(s) to a hydrocarbonchain or being a component of a heterocyclic ring, may be used as sprayliquids.

Aqueous formulations may be prepared from emulsion concentrates, pastesor wettable powders by adding water. To prepare emulsions theingredients as such or dissolved in a solvent may be homogenized inwater or organic solvents by means of wetting or dispersing agents, e.g.polyethylene oxide adducts. Concentrates which are suitable for dilutionwith water may be prepared from active ingredient, emulsifying ordispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients withthe solid carrier, e.g. kieselguhr, talc, clay or fertilizers.

The preparation of the compounds and their use are illustrated in thefollowing examples.

The active ingredients may also be mixed with a fungicide, insecticide,herbicide, growth regulator or soil disinfectant.

EXAMPLE 1 N-3,5-dichlorophenyl-5-methyl-5-vinyloxazolidinedione

35 parts of 3,5-dichlorophenyl isocyanate, 26 parts of ethyl vinyllactate and 5 parts of triethylamine in 600 parts of benzene are keptunder reflux for 6 hours in a stirred aparatus. After the reactionmixture has been concentrated and the triethylamine has been removed, 42parts of colourless crystals are obtained which, after recrystallizationfrom methanol, have a melting point of 104° to 105° C.

EXAMPLE 2N-3,5-dichlorophenyl-5-methyl-5-(1-bromovinyl)-oxazolidinedione

5 parts of potassium tert-butylate is added to 30 parts ofN-3,5-dichlorophenyl-5-(1,2-dibromoethyl)-oxazolidine-2,4-dione (m.p.147° to 149° C) (obtained fromN-3,5-dichlorophenyl-5-methyl-5-vinyloxazolidinedione by reaction withbromine) in 100 parts benzene. The mixture is then stirred for 48 hoursat room temperature. Concentration is carried out after removal of thesalt and base. Colourless crystals are obtained having a melting pointof 90° to 95° C (from hexane).

EXAMPLE 3

The active ingredients are added to a nutrient solution ideally suitedfor promoting the growth of the fungus Aspergillus niger in amounts of100, 75, 50, 25, 10, 5 and 1 part(s) per million parts of nutrientsolution. 20 ml of the nutrient solutionprepared in this manner isplaced in 100 ml Erlenmeyer flasks and inoculated with 0.3 mg of sporesof Aspergillus niger. The flasks are heated for 120 hours at 36° C. Theextent of fungus spread -- predominantly on the surface of the solution-- is subsequently assessed.

    ______________________________________                                                        Amount of ingredient in                                                       nutrient solution in parts                                                    per million parts of solution                                 Active ingredient 100    75    50  25  10  5   1                              ______________________________________                                         ##STR1##         0      0     0   0   0   2   5                               ##STR2##         0      0     0   0   3   3   5                               ##STR3##         0      1     2   2   3   3   5                              (comparative agent)                                                           control (untreated)                                                                             5      5     5   5   5   5   5                              ______________________________________                                         0 = no fungus growth, graduated down to                                       5 = uncontrolled fungus growth (surface of nutrient solution completely       covered by fungus)                                                       

EXAMPLE 4

Leaves of barley seedlings grown in pots are sprayed with aqueousemulsions consisting of 80% active ingredient and 20% emulsifier. Afterthe sprayed layer has dried the leaves are dusted with oidia of barleymildew (Erysiphe graminis var. hordei). The plants are subsequentlyplaced in a greenhouse kept at from 20° to 22° C and having a relativehumidity of 75 to 80%. The extent of fungus spread is assessed after 10days.

    ______________________________________                                                      Leaf attack after spraying with                                               liquor containing active ingre-                                               dient in amounts of                                             Active Ingredient                                                                             0.2%        0.1%                                              ______________________________________                                        Compound 1          0           2                                             Compound 2                                                                             (comparative                                                                             4           5                                                      agent)                                                               Control  untreated) 5                                                         ______________________________________                                         0 = no attack, graduated down to                                              5 = total leaf area covered with fungus                                  

EXAMPLE 5

Leaves of cucumber seedlings grown in pots are sprayed with aqueousemulsions consisting of 80% active ingredient and 20% emulsifier. Afterthe sprayed layer has dried the leaves are dusted with oidia of cucumbermildew (Erysiphe cichoriacearum). The plants are subsequently placed ina greenhouse kept at from 20° to 22° C and having a relative humidity of75 to 80%. The extent of fungus spread is assessed after 10 days.

    ______________________________________                                                      Leaf attack after spraying with                                               liquor containing active ingre-                                               dient in amounts of                                             Active Ingredient                                                                             0.2%        0.1%                                              ______________________________________                                        Compound 1          0           2                                             Compound 2                                                                             (comparative                                                                  agent)     4           5                                             Control  (untreated)                                                                              5                                                         ______________________________________                                         0 = no attack, graduated down to                                              5 = total leaf area covered with fungus                                  

EXAMPLE 6

90 parts by weight of compound 1 is mixed with 10 parts by weight ofN-methyl-α-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

EXAMPLE 7

20 parts by weight of the compound of Example 2 is dissolved in amixture consisting of 80 parts by weight of xylene, 10 parts by weightof the adduct of 8 to 10 moles of ethylene oxide to 1 mole oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide to 1 mole of castor oil. By pouring the solutioninto 100,000 parts by weight of water and uniformly distributing ittherein, an aqueous dispersion is obtained containing 0.02% by weight ofthe active ingredient.

EXAMPLE 8

20 parts by weight of the compound of Example 1 is dissolved in amixture consisting of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 moles ofethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight ofthe adduct of 40 moles of ethylene oxide to 1 mole of castor oil. Bypouring the solution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

EXAMPLE 9

20 parts by weight of the compound of Example 2 is dissolved in amixture consisting of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 moles ofethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight ofthe adduct of 40 moles of ethylene oxide to 1 mole of castor oil. Bypouring the solution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

EXAMPLE 10

20 parts by weight of the compound of Example 1 is well mixed with 3parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 17 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 60 parts by weight of powderedsilica gel, and triturated in a hammer mill. By uniformly distributingthe mixture in 20,000 parts by weight of water, a spray liquid isobtained containing 0.1% by weight of the active ingredient.

EXAMPLE 11

3 parts by weight of compound 1 is intimately mixed with 97 parts byweight of particulate kaolin. A dust is obtained containing 3% by weightof the active ingredient.

EXAMPLE 12

30 parts by weight of compound 1 is intimately mixed with a mixtureconsisting of 92 parts by weight of powdered silica gel and 8 parts byweight of paraffin oil which has been sprayed onto the surface of thissilica gel. A formulation of the active ingredient is obtained havinggood adherence.

We claim:
 1. A process for controlling fungi wherein the objects to beprotected against fungus attack are treated with a fungitoxic amount ofN-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione.